CN111115688B - Zinc ion battery positive electrode material and preparation method and application thereof - Google Patents

Zinc ion battery positive electrode material and preparation method and application thereof Download PDF

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CN111115688B
CN111115688B CN201911241432.0A CN201911241432A CN111115688B CN 111115688 B CN111115688 B CN 111115688B CN 201911241432 A CN201911241432 A CN 201911241432A CN 111115688 B CN111115688 B CN 111115688B
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ion battery
zinc ion
positive electrode
electrode material
zinc
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CN111115688A (en
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罗云峰
傅洋
罗小松
陈璞
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Ruihai Po Qingdao Energy Technology Co ltd
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Priority to JP2022534261A priority patent/JP2023504864A/en
Priority to PCT/CN2020/133159 priority patent/WO2021110000A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a zinc ion battery anode material and a preparation method and application thereof. The method for preparing the positive electrode material of the zinc ion battery comprises the following steps: and sintering the manganese carbonate to obtain the positive electrode material of the zinc ion battery. According to the method, the high-performance zinc ion battery anode material can be obtained by carrying out heat treatment on the manganese carbonate, and the method is low in raw material cost, simple in preparation process and suitable for industrial production.

Description

Zinc ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of zinc ion batteries, in particular to a zinc ion battery positive electrode material and a preparation method and application thereof.
Background
The zinc ion battery is a novel secondary water system battery developed in recent years, has the advantages of high energy density, high power density, efficient and safe discharge process, nontoxic and cheap battery materials, simple preparation process and the like, and has good application value and development prospect in the fields of large-scale energy storage and the like.
Among the reported positive electrode materials for aqueous zinc-ion batteries, lithium manganate and manganese dioxide are mostly used as positive electrode materials for aqueous zinc-ion batteries. Manganese dioxide, a positive electrode material in the existing water-based zinc ion battery, is mostly synthesized by a hydrothermal method, a coprecipitation method, a liquid phase method using potassium permanganate as an oxidant and other preparation methods. However, the specific capacity of the existing lithium manganate cathode material is low, and the cost of raw materials is high. The hydrothermal method, the coprecipitation method, the liquid phase method using potassium permanganate as an oxidant and other synthesis methods adopted by the manganese dioxide anode material of the water-based zinc ion battery are complex in preparation process, low in yield, high in raw material cost and not beneficial to large-scale industrial production.
Therefore, the existing positive electrode material of the zinc ion battery and the preparation method thereof still need to be studied deeply.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a zinc ion battery positive electrode material, and a preparation method and application thereof. The method for preparing the zinc ion battery anode material can obtain the high-performance zinc ion battery anode material by carrying out heat treatment on the manganese carbonate, and is low in raw material cost, simple in preparation process and suitable for industrial production. The method comprises the following steps: and sintering the manganese carbonate to obtain the positive electrode material of the zinc ion battery. According to the method, manganese carbonate is sintered at different temperature sections, and the obtained sintered product can be used as a positive electrode material of a water-based zinc ion battery. Compared with the manganese dioxide anode material prepared by the existing hydrothermal method, potassium permanganate oxidation method and other methods, the method provided by the invention has the advantages of lower raw material cost, simpler preparation process, better electrochemical performance of the product and higher specific capacity.
In addition, the method for preparing the positive electrode material of the zinc-ion battery according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, the sintering process is performed at 150 to 500 ℃.
In some embodiments of the present invention, the sintering process is performed for 0.5 to 20 hours.
In some embodiments of the present invention, the sintering process is performed for 2 to 8 hours.
In another aspect of the invention, the invention provides a positive electrode material of a zinc ion battery. According to the embodiment of the invention, the zinc-ion battery cathode material is prepared by the method for preparing the zinc-ion battery cathode material of the embodiment. Therefore, compared with the manganese dioxide anode material prepared by the existing hydrothermal method, the potassium permanganate oxidation method and other methods, the zinc ion battery anode material has better electrochemical performance and higher specific capacity, and has the advantages of low raw material cost and simple preparation process.
In addition, the method for preparing the positive electrode material of the zinc-ion battery according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the invention, the zinc-ion battery positive electrode material comprises: at least one of sintered manganese carbonate, sintered manganese dioxide and sintered manganese sesquioxide.
In some embodiments of the invention, the positive electrode material of the zinc-ion battery is sintered manganese carbonate, sintered manganese dioxide or sintered manganese sesquioxide.
In yet another aspect, the present invention is directed to a zinc ion battery. According to an embodiment of the present invention, the zinc-ion battery includes: the positive electrode material of the zinc-ion battery of the above example. Therefore, the zinc ion battery has all the characteristics and advantages described in the foregoing for the positive electrode material of the zinc ion battery, and the description is omitted. In general, the zinc ion battery has excellent capacity and cycle performance.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows XRD test results of positive electrode materials of zinc ion batteries prepared in examples 1 to 4;
FIG. 2 shows the results of the cycle performance test of the zinc ion battery made of the positive electrode material of the zinc ion battery prepared in examples 1 to 4 under the condition of a current density of 10 mA/g;
FIG. 3 shows the results of the cycle performance test of the zinc ion batteries made of the positive electrode materials of the zinc ion batteries prepared in examples 1 to 4 under the condition that the current density is 50 mA/g.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Method for preparing positive electrode material of zinc ion battery
In one aspect of the invention, a method of making a positive electrode material for a zinc ion battery is provided. According to an embodiment of the invention, the method comprises: and sintering the manganese carbonate to obtain the positive electrode material of the zinc ion battery. According to the method, manganese carbonate is sintered at different temperature sections, and the obtained sintered product can be used as a positive electrode material of a water-based zinc ion battery. Compared with the manganese dioxide anode material prepared by the existing hydrothermal method, potassium permanganate oxidation method and other methods, the method provided by the invention has the advantages of lower raw material cost, simpler preparation process, better electrochemical performance of the product and higher specific capacity.
The inventor finds that the structure of the material can generate phase transition along with the rise of the sintering temperature of the manganese carbonate, and the phase transition of the structure of the material can be controlled by controlling the sintering temperature and the sintering time, so that a novel cathode material with excellent electrochemical performance is obtained.
According to some embodiments of the present invention, the sintering process is performed at 150 to 500 ℃, and specifically, the sintering temperature may be 150 ℃, 180 ℃, 200 ℃, 230 ℃, 250 ℃, 290 ℃, 320 ℃, 340 ℃, 370 ℃, 420 ℃, 460 ℃, 500 ℃ or the like. By sintering the manganese carbonate under the temperature condition, the performance of the prepared cathode material product can be obviously improved.
According to some embodiments of the present invention, the sintering process is performed at 150-320 ℃, and specifically, the sintering temperature may be 150 ℃, 180 ℃, 200 ℃, 230 ℃, 250 ℃, 290 ℃, 320 ℃, and the like. Thus, MnCO3The sintered product is still MnCO3Phase, but the performance of the sintered product is significantly better than that of the non-heat treated MnCO by the sintering heat treatment3A material.
According to some embodiments of the present invention, the sintering process is performed at 320-360 ℃, specifically, the sintering temperature may be 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, and the like. Thus, MnCO3MnO for sintered product2The phases are dominant. The inventor finds in research that the catalyst is prepared by MnCO3Sintering to obtain MnO2Compared with MnO prepared by a hydrothermal method2And commercially available electrolytic MnO2Zinc ion battery made of positive electrode materialHas better specific capacity.
According to some embodiments of the present invention, the sintering process is performed at 360-500 ℃, and specifically, the sintering temperature may be 360 ℃, 400 ℃, 420 ℃, 450 ℃, 470 ℃, 500 ℃, and the like. Thus, MnCO3The sintered product is Mn2O3。
According to some embodiments of the present invention, the time of the sintering process may be 0.5 to 20 hours, such as 0.5 hour, 1 hour, 2 hours, 5 hours, 8 hours, 10 hours, 15 hours, 20 hours, and the like. Therefore, the performance of the prepared cathode material product can be further improved.
According to some embodiments of the present invention, the sintering process may be performed for 2 to 8 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, and the like. Therefore, the performance of the prepared cathode material product can be further improved.
According to some embodiments of the present invention, the method of preparing a zinc ion positive electrode material described above further comprises: after the sintering process is completed, the sintered product is ground. Therefore, the sintered product can be ground to a target particle size, and the specific target particle size is not particularly limited and can be selected by those skilled in the art according to actual needs.
Zinc ion battery anode material
In another aspect of the invention, the invention provides a positive electrode material of a zinc ion battery. According to the embodiment of the invention, the zinc-ion battery cathode material is prepared by the method for preparing the zinc-ion battery cathode material of the embodiment. Therefore, compared with the manganese dioxide anode material prepared by the existing hydrothermal method, the potassium permanganate oxidation method and other methods, the zinc ion battery anode material has better electrochemical performance and higher specific capacity, and has the advantages of low raw material cost and simple preparation process.
According to some embodiments of the invention, the above zinc-ion battery positive electrode material comprises: at least one of sintered manganese carbonate, sintered manganese dioxide and sintered manganese sesquioxide. Specifically, the sintered manganese carbonate can be prepared by sintering commercially available manganese carbonate at 150-350 ℃; the manganese dioxide after sintering can be prepared by sintering commercially available manganese carbonate at 320-360 ℃; the sintered manganese sesquioxide can be prepared by sintering commercially available manganese carbonate at 360-500 ℃;
according to some embodiments of the invention, the positive electrode material of the zinc-ion battery is sintered manganese carbonate, sintered manganese dioxide or sintered manganese sesquioxide.
Zinc ion battery
In yet another aspect, the present invention is directed to a zinc ion battery. According to an embodiment of the present invention, the zinc-ion battery includes: the positive electrode material of the zinc-ion battery of the above example. Therefore, the zinc ion battery has all the characteristics and advantages described in the foregoing for the positive electrode material of the zinc ion battery, and the description is omitted. In general, the zinc ion battery has excellent capacity and cycle performance.
According to an embodiment of the invention, the zinc-ion battery comprises a positive plate, a diaphragm, a negative plate and electrolyte. Specifically, the positive plate comprises the positive electrode material of the zinc ion battery in the embodiment, and auxiliary materials such as a conductive agent and a binder which are common in the field. The negative plate can be a zinc foil or a zinc powder negative electrode prepared by adopting copper mesh current collector slurry drawing. The specific kind of the separator is not particularly limited, and an aqueous solution mainly containing zinc sulfate may be used as the electrolyte.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Manganese carbonate is used as a raw material and is put into a box type furnace for heat treatment, the sintering temperature is 320 ℃, and the sintering time is 4 hours.
(2) After the anode material is cooled to room temperature, taking out the material, grinding the material by using an agate mortar to obtain an anode material, and detecting by XRD (X-ray diffraction), wherein the material is MnCO3。
(3) Manufacturing a battery positive pole piece: homogenizing according to the proportion of acetylene black to PVDF (polyvinylidene fluoride) to 7:2:1, then uniformly coating the uniformly stirred positive electrode slurry on a conductive PE (polyethylene) membrane, and putting the conductive PE membrane into an oven for vacuum drying at the drying temperature of 60 ℃ for 10 h.
(4) Assembling the battery: and (3) positive electrode: preparing the anode material obtained in the step; negative electrode: a zinc foil;
a diaphragm: an adsorption glass fiber mat type separator (AGM separator); electrolyte solution: zinc sulfate aqueous solution with concentration of 1.8mol/L
And (3) fully soaking the AGM diaphragm in a liquid electrolyte, and then combining the positive electrode material and the negative electrode Zn foil to assemble the battery.
(5) And (3) testing the battery: the specific capacity of the zinc ion battery under the environment of 25 ℃ and the current density of 10mA/g is 277 mA/h/g.
The specific capacity of the zinc ion battery at the current density of 50mA/g under the environment of 25 ℃ is 173 mA.h/g.
The XRD test result of the cathode material is shown in figure 1, and the cycle performance of the battery is shown in figures 2 and 3.
Example 2
A positive electrode material was prepared and tested as a battery in substantially the same manner as in example 1, except that the sintering temperature was 340 ℃ and the positive electrode material obtained was MnO as measured by XRD2。
And (3) testing the battery: the specific capacity of the zinc ion battery under the environment of 25 ℃ and the current density of 10mA/g is 282 mA.h/g.
The specific capacity of the zinc ion battery at the current density of 50mA/g under the environment of 25 ℃ is 187 mA/h/g.
The XRD test result of the cathode material is shown in figure 1, and the cycle performance of the battery is shown in figures 2 and 3.
Example 3
A positive electrode material was prepared and tested by forming a cell in substantially the same manner as in example 1, except that the sintering temperature was 370 ℃ and the obtained positive electrode material was Mn as measured by XRD2O3。
And (3) testing the battery: the specific capacity of the zinc ion battery under the environment of 25 ℃ and the current density of 10mA/g is 135 mA.h/g.
The specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 96 mA.h/g.
The XRD test result of the cathode material is shown in figure 1, and the cycle performance of the battery is shown in figures 2 and 3.
Example 4
A positive electrode material was prepared and tested by forming a cell in substantially the same manner as in example 1, except that the sintering temperature was 420 ℃ and the positive electrode material obtained was Mn as measured by XRD2O3。
And (3) testing the battery: the specific capacity of the zinc ion battery under the environment of 25 ℃ and the current density of 10mA/g is 110 mA.h/g.
The specific capacity of the zinc ion battery at the current density of 50mA/g under the environment of 25 ℃ is 95 mA.h/g.
The XRD test result of the cathode material is shown in figure 1, and the cycle performance of the battery is shown in figures 2 and 3.
Comparative example 1
Using commercial MnCO which has not been heat-treated3As a positive electrode material, a zinc ion battery was produced in the same manner as in example 1 and was tested.
The specific capacity of the zinc ion battery under the environment of 25 ℃ and the current density of 10mA/g is 85 mA.h/g.
The specific capacity of the zinc ion battery at the current density of 50mA/g under the environment of 25 ℃ is 73 mA.h/g.
The test results show that the heat treated MnCO is compared with that of example 13Material, not heat-treated MnCO3The specific capacity of the zinc ion battery made is significantly lower, which is probably due to MnCO caused by sintering treatment3The crystallinity of the manganese ion is deteriorated, so that the manganese ion is easier to be extracted and embedded, and better specific capacity is obtained.
Comparative example 2
1.7384g of potassium permanganate (0.011mol) and 0.7437g of manganese sulfate monohydrate (0.0044mol) are weighed and dissolved in 80mL of deionized water, the mixture is magnetically stirred for 2 hours to form a uniform solution, and then the solution is transferred to a stainless steel hydrothermal reaction kettle with the volume of 100mL and is kept at 160 ℃ for 12 hours. Then carrying out vacuum filtration on the product, washing the product with deionized water, and drying the product in a 60 ℃ drying oven for 8 hours to obtain MnO2And (3) a positive electrode material. The positive electrode material was fabricated into a zinc ion battery in the same manner as in example 1 and tested.
The specific capacity of the zinc ion battery at the current density of 10mA/g under the environment of 25 ℃ is 156 mA.h/g.
The specific capacity of the zinc ion battery at the current density of 50mA/g under the environment of 25 ℃ is 120 mA.h/g.
The test results show that MnO was obtained as compared with the preparation by sintering treatment in example 22Materials, MnO prepared in hydrothermal kettle in comparative example 22The specific capacity of the zinc ion battery made of the material is obviously lower.
Comparative example 3
Using commercially available electrolytic MnO2As a positive electrode material, a zinc ion battery was produced in the same manner as in example 1 and was tested.
The specific capacity of the zinc ion battery under the environment of 25 ℃ and the current density of 10mA/g is 78 mA.h/g.
The specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 62 mA.h/g.
The test results show that MnO was obtained as compared with the preparation by sintering treatment in example 22Material, commercially available electrolytic MnO used in comparative example 32The specific capacity of the zinc ion battery made of the material is obviously lower.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (1)

1. A zinc-ion battery, comprising: the zinc ion battery positive electrode material is sintered manganese carbonate, and is obtained by sintering the manganese carbonate at the temperature of 150-320 ℃.
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JP2022534261A JP2023504864A (en) 2019-12-06 2020-12-01 Cathode material for zinc ion battery, its preparation method and use
PCT/CN2020/133159 WO2021110000A1 (en) 2019-12-06 2020-12-01 Zinc ion battery positive electrode material, preparation method therefor, and application thereof
KR1020227021045A KR20220104216A (en) 2019-12-06 2020-12-01 Zinc-ion battery positive electrode material, its manufacturing method and application
US17/832,691 US20220302446A1 (en) 2019-12-06 2022-06-06 Zinc ion battery positive electrode material, preparation method therefor, and application thereof

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CN111115688B (en) * 2019-12-06 2022-02-15 瑞海泊(青岛)能源科技有限公司 Zinc ion battery positive electrode material and preparation method and application thereof
CN114229904B (en) * 2021-12-06 2023-06-23 桂林理工大学 Mn for water-based zinc ion battery 2 O 3 /Mn 3 O 4 Preparation method of composite electrode material
CN114314670B (en) * 2021-12-29 2022-09-13 西北大学 Modification method of copper ion implanted zinc battery anode material delta-manganese dioxide
CN114538521B (en) * 2022-01-14 2023-10-13 福州大学 Potassium-doped oxygen vacancy manganese dioxide positive electrode material and preparation method and application thereof

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CN111115688B (en) * 2019-12-06 2022-02-15 瑞海泊(青岛)能源科技有限公司 Zinc ion battery positive electrode material and preparation method and application thereof

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